Thick film materials are mixtures of metals, metallic oxides, glass and/or ceramic powders dispersed in an organic medium. These materials, which are applied to nonconductive substrates to form conductive, resistive or insulating films, are used in a wide variety of electronic and light electrical components.
The properties of such thick film compositions depend on the specific constituents of the compositions. Most of such thick film compositions contain three major components. A conductive phase determines the electrical properties and influences the mechanical properties of the final film. A binder, usually a glass and/or crystalline oxide, holds the thick film together and bonds it to a substrate, and an organic medium (vehicle) acts as a dispersing medium and influences the application characteristcs of the composition and particularly its rheology.
High stability and low process sensitivity are critical requirements for thick film resistors in microcircuit applications. In particular, it is necessary that resistivity (R.sub.av) of a resistor be stable over a wide range of temperature conditions. Thus, the thermal coefficient of resistance (TCR) is a critical variable in any thick film resistor. Because thick film resistor compositions are comprised of a functional (conductive) phase and a permanent binder phase, the properties of the conductive and binder phases and their interactions with each other and with the substrate affect both resistivity and TCR.
Glass is most frequently used as the inorganic binder for thick film resistors. Frequently used glass frits have been borosilicate frits, such as barium, calcium or other alkaline earth borosilicate frits. The preparation of such glass frits is well known and consists, for example, in melting together the constituents of the glass in the form of their oxides and pouring such molten composition into water to form the frit. The batch ingredients may, of course, be any compound that will yield the desired oxides under the usual conditions of frit production. For example, boric oxide will be obtained from boric acid; silicon dioxide will be produced from flint; barium oxide will be produced from barium carbonate; etc. The glass is preferably milled in a ball mill with water to reduce the particle size of the frit and to obtain a frit of substantially uniform size.
Despite the wide variety of glasses which have been used as a binder for thick film resistor materials, it has heretofore been difficult to manufacture thick film resistors over a wide range of resistance values using tin oxide pyrochlore-based resistor materials. In particular, there is a significant need for inorganic binder materials with which such pyrochlore-based materials can be formulated to make high end resistors, i.e., those having resistance values in the range of 50 k.OMEGA./.quadrature. to 100M .OMEGA./.quadrature..